EP3103796B1 - Novel compound and epoxy resin composition containing same - Google Patents
Novel compound and epoxy resin composition containing same Download PDFInfo
- Publication number
- EP3103796B1 EP3103796B1 EP15745854.8A EP15745854A EP3103796B1 EP 3103796 B1 EP3103796 B1 EP 3103796B1 EP 15745854 A EP15745854 A EP 15745854A EP 3103796 B1 EP3103796 B1 EP 3103796B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- epoxy resin
- resin composition
- acid
- pack type
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000647 polyepoxide Polymers 0.000 title claims description 54
- 239000003822 epoxy resin Substances 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 title claims description 44
- 150000001875 compounds Chemical class 0.000 title claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 21
- -1 carboxylate anion Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000000123 paper Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- ABNDDOBSIHWESM-UHFFFAOYSA-N 1-methyl-5,6-dihydro-4h-pyrimidine Chemical compound CN1CCCN=C1 ABNDDOBSIHWESM-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 0 C[n]1c(*)nc(*)c1* Chemical compound C[n]1c(*)nc(*)c1* 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WAHBMPYCNRZYBV-UHFFFAOYSA-N (3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl 2-methylcyclohexane-1-carboxylate Chemical compound CC1CCCCC1C(=O)OCC1C(C)CC2OC2C1 WAHBMPYCNRZYBV-UHFFFAOYSA-N 0.000 description 1
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2,2-bis(2-hydroxyphenyl)propane Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PEHXKUVLLWGBJS-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=CC=C(O)C=1C(C)C1=CC=CC=C1O PEHXKUVLLWGBJS-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VEGUCZXWLYWJFN-UHFFFAOYSA-N 3-[(3-hydroxy-2-methylphenyl)methyl]-2-methylphenol Chemical compound CC1=C(O)C=CC=C1CC1=CC=CC(O)=C1C VEGUCZXWLYWJFN-UHFFFAOYSA-N 0.000 description 1
- ZUESTMNQCYNCPP-UHFFFAOYSA-N 3-[2-(3-hydroxy-2-methylphenyl)propan-2-yl]-2-methylphenol Chemical compound CC1=C(O)C=CC=C1C(C)(C)C1=CC=CC(O)=C1C ZUESTMNQCYNCPP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- OXRFNJSKALBWCF-UHFFFAOYSA-N 4-[4,4-bis(4-hydroxyphenyl)butan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 OXRFNJSKALBWCF-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- MQHAJJKQGSCYMY-ARJAWSKDSA-N C/C(/N)=C/NC(C)=O Chemical compound C/C(/N)=C/NC(C)=O MQHAJJKQGSCYMY-ARJAWSKDSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- This invention relates to an epoxy resin composition containing a specific dicyanamide salt and a one-pack type thermosetting epoxy resin composition containing the salt and having excellent storage stability and curability.
- Epoxy resins exhibit high adhesion to various substrates. Cured products of epoxy resins have relatively excellent properties, such as heat resistance, chemical resistance, electric characteristics, and mechanical characteristics, and are useful in a wide range of applications, including coatings, adhesives, and molding materials.
- a two-pack type epoxy resin composition is characterized by curability at ambient or low temperature. Nevertheless, a two-pack epoxy resin composition is disadvantageous in that the two packs must be metered and mixed immediately before use and that the pot life of the composition is short and therefore has a limited use, for example, meeting difficulty in applying to automatic machinery. To eliminate these disadvantages, a one-pack type epoxy resin composition has been demanded.
- Latent curing agents so far proposed include dicyandiamide, dibasic acid hydrazides, amine-boron trifluoride complex salts, guanamines, melamine, and imidazoles. They have, however, their own disadvantages. That is, mixtures of en epoxy resin with dicyandiamide, melamine, or guanamines are, while excellent in storage stability, problematic in that they need a high temperature (150°C or higher) and a long time to cure.
- compositions containing a dibasic acid dihydrazide or an imidazole cure at relatively low temperatures but have poor storage stability.
- compositions containing an amine-boron trifluoride complex salt have high storage stability and cure in short times, they are poor in water resistance and corrosive to metals.
- Patent Document 1 proposes using an ionic liquid composed of, e.g., a combination of an ammonium- or phosphonium-based cation and a carboxylate anion as an epoxy resin curing agent. The results are still unsatisfactory.
- Patent Document 1 US 2009/0030158 US 4,761,466 discloses an adhesive composition comprising a mixture of a polyepoxide, an amine curing agent and a particular thiocyanate salt.
- WO 2012/042673 A1 discloses a two-pack curable epoxy resin coating composition for a floor member containing, in relation to 100 parts by mass of an epoxy resin (component (a)), 10 to 75 parts by mass of a vinyl monomer and/or a (meth)acrylate monomer (component (b)), 0 to 50 parts by mass of a denaturant (component (c)), 0 to 50 parts by mass of an epoxy (meth)acrylate (component (d)), and 15 to 45 parts by mass of a curing agent (component (e)); and 0.5 to 10 parts by mass of an ionic liquid (component (f)) in relation to 100 parts by mass of the sum of components (a) to (e).
- An object of the invention is to provide an epoxy resin composition excellent in storage stability and curability.
- the invention provides an epoxy resin composition containing (A) an epoxy resin and (B) at least one of compounds represented by general formulae (1-1), (1-3), (1-4) or (1-5): wherein R2', R3, R4, R5, R9, R10, R11, R12, R13, R14, and R15 each independently represent a hydrogen atom, an alkyl group, or an aryl group; and X represents a dicyanamide ion.
- the invention provides a practically useful epoxy resin composition that is composed of easily available components and exhibits moderate curing characteristics and storage stability in good balance.
- the invention provides a one-pack type epoxy resin composition free from a curing resin component that is solid at ambient temperature, so that the resin composition has excellent workability and is suitable for application to tight, hard-to-reach places or impregnation application.
- Examples of the alkyl group as represented by R2', R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 in general formulae (1-1) through (I-5) include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, t-octyl, nonyl, and decyl.
- Examples of the aryl group as represented by R2', R3, R4, R5, R6, R7, R8, R9, RIO, R11, R12, R13, R14, and R15 include those having 6 to 12 carbon atoms, such as phenyl and naphthyl.
- the compound having general formula (I) in which X is a dicyanamide ion can be prepared by adding an acidic substance, such as hydrochloric acid, to a nitrogen-containing heterocyclic compound corresponding to a desired cation structure to form an intermediate (1-1), which is then caused to react with sodium dicyandiamide or a dicyandiamide salt in the presence of an alcohol or water as shown in the following reaction scheme: wherein R1 represents the partial cyclic structure of compounds represented by the above-mentioned general formulae (1-1), (1-3), (1-4) and (1-5); and R2, and R3 are the same groups as R2' and R3 in the above-mentioned general formulae (1-1), (1-3), (1-4) and (1-5).
- an acidic substance such as hydrochloric acid
- Examples of the epoxy resin that can be used in the epoxy resin composition of the invention as component (A) include polyglycidyl ethers of mononuclear polyhydric phenol compounds, such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; polyglycidyl ethers of polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (i.e., bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (i.e., bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3 -bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphen
- polyepoxy compounds may be internally crosslinked by an isocyanate-terminated prepolymer or may have their molecular weight increased using a polyfunctional polyhydric active hydrogen compound, e.g., a polyhydric phenol, a polyamine, a carbonyl-containing compound, or a polyphosphoric ester.
- a polyfunctional polyhydric active hydrogen compound e.g., a polyhydric phenol, a polyamine, a carbonyl-containing compound, or a polyphosphoric ester.
- Preferred of the recited epoxy resins (A) are polyglycidyl ethers of polynuclear polyhydric phenol compounds in terms of workability and curability, with bisphenol F and bisphenol A being more preferred.
- the epoxy resin (A) preferably has an epoxy equivalent of from 70 to 3,000, more preferably 90 to 2,000. With an epoxy equivalent less than 70, the physical properties of the cured product can reduce. With an epoxy equivalent larger than 3,000, curability can be insufficient.
- Component (B) that can be used in the epoxy resin composition of the invention is at least one of the compounds represented by general formulae (I-1), (1-3), (1-4) and (1-5), the examples of which have been described.
- the amount of the compound (B) of formula (I) used in the epoxy resin composition of the invention is preferably 0.1 to 50 parts, more preferably 1 to 20 parts, by mass per 100 parts by mass of the epoxy resin (A). If the content of compound (B) is less than 0.1 parts, insufficient cure can result. If it exceeds 50 parts, the storage stability of the epoxy resin composition can be impaired considerably.
- the epoxy resin composition may contain commonly used additives, including other curing agents except the compound (B) of at least one of formulae (I-1), (1-3), (1-4) and (1-5); curing catalysts; reactive or nonreactive diluents (plasticizers), such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments, such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous materials; silane coupling agents, such as ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)-N
- the epoxy resin composition of the invention can be used for a wide range of applications, such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive wallpaper, and adhesive flooring; processed paper, such as art paper, light-weight coated paper, cast-coated paper, coated paperboard, carbonless copy paper, and impregnated paper; textile processing agents, such as sizing agents, anti-fray agents, and processing agents for natural fibers, synthetic fibers, glass fiber, carbon fiber, and metal fibers; building materials, such as sealants, cement admixtures, and waterproof materials; and sealants for electronic/electric devices.
- applications such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive wallpaper,
- One-pack type epoxy resin composition A-1 was prepared by uniformly mixing 340 g of Adeka Resin EP-4100L from Adeka Corp. (bisphenol A diglycidyl ether epoxy resin; epoxy equivalent: 170 g/eq.; total chlorine content: 600 ppm) with 15 g of curing agent A-1, followed by thoroughly defoaming under reduced pressure at room temperature.
- Adeka Resin EP-4100L bisphenol A diglycidyl ether epoxy resin; epoxy equivalent: 170 g/eq.; total chlorine content: 600 ppm
- One-pack type epoxy resin composition B-1 was prepared in the same manner as in Example 4, except for using 17.7 g of curing agent B-1.
- One-pack type epoxy resin composition C-1 was prepared in the same manner as in Example 4-1, except for using 16.5 g of curing agent C-1.
- One-pack type epoxy resin composition D was prepared in the same manner as in Example 4-1, except for using 8.2 g of 1-methylimidazole.
- One-pack type epoxy resin composition E was prepared in the same manner as in Example 4-1, except for using 11 g of 2-ethyl-4-methylimidazole.
- One-pack type epoxy resin composition D was prepared in the same manner as in Example 4-1, except for using 9.8 g of 1-methyl-1,4,5,6-tetrahydropyrimidine.
- the one-pack type epoxy resin compositions obtained in Examples and Comparative Examples were evaluated for physical properties in accordance with the following methods.
- the one-pack type epoxy resin composition was stored hermetically at 40°C immediately after the preparation. The time required for the composition to lose flowability was recorded as a measure for evaluating one-pack stability.
- the one-pack type epoxy resin composition was caused to gel on a hot plate at 150°C and 180°C. The gelling time was recorded to evaluate curability.
- Example 4-1 Comp.
- Example 1 Example 5-1 Comp.
- Example 2 Example 6-1 Comp.
- Example 3 One-pack Stability (hr) 48 12 48 6 >200 72 Gel Time (min) 150°C 1'45" 1'55" 1'10" 1'12" >60 >60 180°C 0'45" 0'48" 0'30" 0'30" 35 >60
- the use of the nitrogen-containing salt compound having a dicyanamide anion structure as a thermosetting type latent curing agent for epoxy resins provides a one-pack type epoxy resin composition excellent in not only one-pack stability but curability.
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Description
- This invention relates to an epoxy resin composition containing a specific dicyanamide salt and a one-pack type thermosetting epoxy resin composition containing the salt and having excellent storage stability and curability.
- Epoxy resins exhibit high adhesion to various substrates. Cured products of epoxy resins have relatively excellent properties, such as heat resistance, chemical resistance, electric characteristics, and mechanical characteristics, and are useful in a wide range of applications, including coatings, adhesives, and molding materials.
- Conventional epoxy resin compositions are mostly of two-pack type in which an epoxy resin component is mixed with a curing agent or a curing accelerator on use. A two-pack type epoxy resin composition is characterized by curability at ambient or low temperature. Nevertheless, a two-pack epoxy resin composition is disadvantageous in that the two packs must be metered and mixed immediately before use and that the pot life of the composition is short and therefore has a limited use, for example, meeting difficulty in applying to automatic machinery. To eliminate these disadvantages, a one-pack type epoxy resin composition has been demanded.
- In order to develop a one-pack type curing resin composition, a curing agent that does not react at room temperature but commences reaction to cure upon heating, i.e., a latent curing agent is necessary. Latent curing agents so far proposed include dicyandiamide, dibasic acid hydrazides, amine-boron trifluoride complex salts, guanamines, melamine, and imidazoles. They have, however, their own disadvantages. That is, mixtures of en epoxy resin with dicyandiamide, melamine, or guanamines are, while excellent in storage stability, problematic in that they need a high temperature (150°C or higher) and a long time to cure. It is widely practiced to use a curing accelerator in combination to shorten the curing time, but this is accompanied by remarkable reduction in storage stability. On the other hand, compositions containing a dibasic acid dihydrazide or an imidazole cure at relatively low temperatures but have poor storage stability. While compositions containing an amine-boron trifluoride complex salt have high storage stability and cure in short times, they are poor in water resistance and corrosive to metals.
- Patent Document 1 below proposes using an ionic liquid composed of, e.g., a combination of an ammonium- or phosphonium-based cation and a carboxylate anion as an epoxy resin curing agent. The results are still unsatisfactory.
- Patent Document 1:
US 2009/0030158
US 4,761,466 discloses an adhesive composition comprising a mixture of a polyepoxide, an amine curing agent and a particular thiocyanate salt.
WO 2012/042673 A1 discloses a two-pack curable epoxy resin coating composition for a floor member containing, in relation to 100 parts by mass of an epoxy resin (component (a)), 10 to 75 parts by mass of a vinyl monomer and/or a (meth)acrylate monomer (component (b)), 0 to 50 parts by mass of a denaturant (component (c)), 0 to 50 parts by mass of an epoxy (meth)acrylate (component (d)), and 15 to 45 parts by mass of a curing agent (component (e)); and 0.5 to 10 parts by mass of an ionic liquid (component (f)) in relation to 100 parts by mass of the sum of components (a) to (e). - An object of the invention is to provide an epoxy resin composition excellent in storage stability and curability.
- As a result of extensive investigations with a view to accomplishing the above object, the inventors have found a specific dicyanamide salt exhibits excellent effects as an epoxy resin curing agent and achieved the object of the invention. The invention has been completed based on this finding.
- The invention provides an epoxy resin composition containing (A) an epoxy resin and (B) at least one of compounds represented by general formulae (1-1), (1-3), (1-4) or (1-5):
- The invention provides a practically useful epoxy resin composition that is composed of easily available components and exhibits moderate curing characteristics and storage stability in good balance. In particular, the invention provides a one-pack type epoxy resin composition free from a curing resin component that is solid at ambient temperature, so that the resin composition has excellent workability and is suitable for application to tight, hard-to-reach places or impregnation application.
-
-
Fig. 1 is a 1H-NMR spectrum of curing agent B-1 (compound No. 2-1) prepared in Example 2-1. -
Fig. 2 is a 13C-NMR spectrum of curing agent B-1 (compound No. 2-1) prepared in Example 2-1. - The invention will be described in detail with reference to its preferred embodiments.
- Examples of the alkyl group as represented by R2', R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 in general formulae (1-1) through (I-5) include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, t-octyl, nonyl, and decyl. Examples of the aryl group as represented by R2', R3, R4, R5, R6, R7, R8, R9, RIO, R11, R12, R13, R14, and R15 include those having 6 to 12 carbon atoms, such as phenyl and naphthyl.
-
- While not being limited, the compound having general formula (I) in which X is a dicyanamide ion can be prepared by adding an acidic substance, such as hydrochloric acid, to a nitrogen-containing heterocyclic compound corresponding to a desired cation structure to form an intermediate (1-1), which is then caused to react with sodium dicyandiamide or a dicyandiamide salt in the presence of an alcohol or water as shown in the following reaction scheme:
- The epoxy resin composition of the invention will next be described.
- Examples of the epoxy resin that can be used in the epoxy resin composition of the invention as component (A) include polyglycidyl ethers of mononuclear polyhydric phenol compounds, such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; polyglycidyl ethers of polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (i.e., bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (i.e., bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3 -bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, and terpenediphenol; polyglycidyl ethers of polyhydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A ethylene oxide adducts; homo- or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids, such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and glycidyl methacrylate; epoxy compounds having a glycidylamino group, such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl o-toluidine; epoxidized cyclic olefin compounds, such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-
epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers, such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds, such as triglycidyl isocyanurate. These polyepoxy compounds may be internally crosslinked by an isocyanate-terminated prepolymer or may have their molecular weight increased using a polyfunctional polyhydric active hydrogen compound, e.g., a polyhydric phenol, a polyamine, a carbonyl-containing compound, or a polyphosphoric ester. - Preferred of the recited epoxy resins (A) are polyglycidyl ethers of polynuclear polyhydric phenol compounds in terms of workability and curability, with bisphenol F and bisphenol A being more preferred.
- The epoxy resin (A) preferably has an epoxy equivalent of from 70 to 3,000, more preferably 90 to 2,000. With an epoxy equivalent less than 70, the physical properties of the cured product can reduce. With an epoxy equivalent larger than 3,000, curability can be insufficient.
- Component (B) that can be used in the epoxy resin composition of the invention is at least one of the compounds represented by general formulae (I-1), (1-3), (1-4) and (1-5), the examples of which have been described.
- The amount of the compound (B) of formula (I) used in the epoxy resin composition of the invention is preferably 0.1 to 50 parts, more preferably 1 to 20 parts, by mass per 100 parts by mass of the epoxy resin (A). If the content of compound (B) is less than 0.1 parts, insufficient cure can result. If it exceeds 50 parts, the storage stability of the epoxy resin composition can be impaired considerably.
- If necessary, the epoxy resin composition may contain commonly used additives, including other curing agents except the compound (B) of at least one of formulae (I-1), (1-3), (1-4) and (1-5); curing catalysts; reactive or nonreactive diluents (plasticizers), such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments, such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous materials; silane coupling agents, such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyl triethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxy silane, and γ-mercaptopropyltrimethoxysilane; lubricants, such as candelilla wax, carnauba wax, Japan wax, insect wax, beeswax, lanolin, spermaceti wax, montan wax, petroleum wax, fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; UV absorbers; flame retardants; defoamers; rust inhibitors; colloidal silica, and colloidal alumina. Adhesive resins, such as xylene resin and petroleum resins, may be used in combination.
- The epoxy resin composition of the invention can be used for a wide range of applications, such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive wallpaper, and adhesive flooring; processed paper, such as art paper, light-weight coated paper, cast-coated paper, coated paperboard, carbonless copy paper, and impregnated paper; textile processing agents, such as sizing agents, anti-fray agents, and processing agents for natural fibers, synthetic fibers, glass fiber, carbon fiber, and metal fibers; building materials, such as sealants, cement admixtures, and waterproof materials; and sealants for electronic/electric devices.
- The invention will now be illustrated in greater detail with reference to Preparation Examples and Examples.
- In 40 ml of water was dissolved 1.8 g (20 mmol) of sodium dicyanamide. While stirring at 25°C, 200 g (20 mmol) of a 0.1 M silver nitrate aqueous solution was added thereto dropwise to cause reaction for 2 hours. The precipitate formed was collected by filtration and dried to give 3.3 g of intermediate A-1 (Ag+N(CN)2 -) as pale yellow powder.
- In 40 ml of water was dissolved 1.6 g (20 mmol) of sodium thiocyanate. While stirring at 25°C, 200 g (20 mmol) of a 0.1 M silver nitrate aqueous solution was added thereto dropwise to cause reaction for 2 hours. The precipitate formed was collected by filtration and dried to give 2.3 g of intermediate A-2 (Ag+(SCN)-) as pale yellow powder.
- In 55 ml of methanol was dissolved 4.5 g (55 mmol) of 1-methylimidazole. While stirring at 25°C, 5.8 g (55 mmol) of a 35% hydrochloric acid aqueous solution was added thereto dropwise to cause reaction for 1 hour. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to give 6.6 g of intermediate B (a compound represented by the formula below) as pale brown solid.
- In 43 ml of methanol was dissolved 4.7 g (43 mmol) of 2-ethyl-4-methylimidazole. While stirring at 25°C, 4.5 g (43 mmol) of a 35% hydrochloric acid aqueous solution was added thereto dropwise to cause reaction for 1 hour. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to give 5.9 g of intermediate C (a compound represented by the formula below) as pale yellow powder.
- In 26 ml of methanol was dissolved 2.6 g (26 mmol) of 1-methyl-1,4,5,6-tetrahydropyrimidine. While stirring at 25°C, 2.7 g (26 mmol) of a 35% hydrochloric acid aqueous solution was added thereto dropwise to cause reaction for 1 hour. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to give 3.7 g of intermediate D (a compound represented by the formula below) as pale yellow powder.
- In 17 ml of water was dissolved 1.0 g (8.5 mmol) of intermediate B. While stirring at 25°C, 1.5 g (8.5 mmol) of intermediate A-1 was added thereto in divided portions to cause reaction for 24 hours. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to furnish 1.2 g of curing agent A-1 as pale yellow liquid.
- In 20 ml of water was dissolved 1.5 g (10.0 mmol) of intermediate C. While stirring at 25°C, 1.7 g (10.0 mmol) of intermediate A-1 was added thereto in divided portions to cause reaction for 24 hours. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to furnish 1.7 g of curing agent B as pale yellow powder. The resulting curing agent B-1 was identified by 1H-NMR and 13C-NMR. The resulting 1H-NMR and 13C-NMR spectra are shown in
Figs. 1 and2 , respectively. - 1H-NMR (400 MHz, CD3OD) d: 1.36 (3H, t, J = 7.6 Hz), 2.29 (3H, d, J = 1.0 Hz), 2.92 (2H, q, J = 7.7 Hz), 7.05 (1H, s)
13C-NMR (100 MHz, CD3OD) d: 8.4, 10.3, 19.0, 114.7, 119.1, 129.1, 148.3 - In 40 ml of water was dissolved 1.2 g (9.2 mmol) of intermediate D. While stirring at 25°C, 1.6 g (9.2 mmol) of intermediate A-1 was added thereto in divided portions to cause reaction for 24 hours. The solvent was removed on an evaporator, and the residue was dried under reduced pressure to afford 1.4 g of curing agent C-1 as pale yellow liquid.
- One-pack type epoxy resin composition A-1 was prepared by uniformly mixing 340 g of Adeka Resin EP-4100L from Adeka Corp. (bisphenol A diglycidyl ether epoxy resin; epoxy equivalent: 170 g/eq.; total chlorine content: 600 ppm) with 15 g of curing agent A-1, followed by thoroughly defoaming under reduced pressure at room temperature.
- One-pack type epoxy resin composition B-1 was prepared in the same manner as in Example 4, except for using 17.7 g of curing agent B-1.
- One-pack type epoxy resin composition C-1 was prepared in the same manner as in Example 4-1, except for using 16.5 g of curing agent C-1.
- One-pack type epoxy resin composition D was prepared in the same manner as in Example 4-1, except for using 8.2 g of 1-methylimidazole.
- One-pack type epoxy resin composition E was prepared in the same manner as in Example 4-1, except for using 11 g of 2-ethyl-4-methylimidazole.
- One-pack type epoxy resin composition D was prepared in the same manner as in Example 4-1, except for using 9.8 g of 1-methyl-1,4,5,6-tetrahydropyrimidine.
- The one-pack type epoxy resin compositions obtained in Examples and Comparative Examples were evaluated for physical properties in accordance with the following methods.
- The one-pack type epoxy resin composition was stored hermetically at 40°C immediately after the preparation. The time required for the composition to lose flowability was recorded as a measure for evaluating one-pack stability.
- The one-pack type epoxy resin composition was caused to gel on a hot plate at 150°C and 180°C. The gelling time was recorded to evaluate curability.
-
Table 1 Example 4-1 Comp. Example 1 Example 5-1 Comp. Example 2 Example 6-1 Comp. Example 3 One-pack Stability (hr) 48 12 48 6 >200 72 Gel Time (min) 150°C 1'45" 1'55" 1'10" 1'12" >60 >60 180°C 0'45" 0'48" 0'30" 0'30" 35 >60 - As is apparent from the results in Table 1, the use of the nitrogen-containing salt compound having a dicyanamide anion structure as a thermosetting type latent curing agent for epoxy resins provides a one-pack type epoxy resin composition excellent in not only one-pack stability but curability.
Claims (2)
- An epoxy resin composition comprising (A) an epoxy resin and (B) at least one of compounds represented by general formulae (1-1), (1-3), (1-4) or (1-5):
- The epoxy resin composition of claim 1, being a one-pack type thermosetting epoxy resin composition.
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KR20140002355A (en) | 2012-06-29 | 2014-01-08 | 삼성전기주식회사 | Inductor and process for producing the same |
JP6240940B2 (en) | 2014-02-06 | 2017-12-06 | 株式会社Adeka | Epoxy resin composition |
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TWI646086B (en) | 2019-01-01 |
US10253136B2 (en) | 2019-04-09 |
CN105916844B (en) | 2018-09-11 |
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US20160333138A1 (en) | 2016-11-17 |
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